Chiral compounds, their synthesis and use as a support

Abstract

The invention relates to a method which comprises synthesising bifunctional compounds then chiral compounds from the bifunctional compounds, also to synthesising supports comprising these chiral compounds, and the use of these supports for preparing or separating enantiomers, or for asymmetric synthesis. The invention also relates to bifunctional compounds, their use as a source of functionalised polymers, and to the chiral compounds, also to the use of these chiral compounds in a chiral support in the form of a three-dimensional network or for separating or preparing enantiomers, principally for analytical or preparative chromatography, and in a support for the production of chiral molecules by asymmetric synthesis.

What is claimed is:  
     
       1. A chiral compound obtained by reaction of at least one hydrogen of an alcohol, amine, or thiol function of at least one chiral unit of a product with at least one group Q of a bifunctional alkenoxyaryl or alkenylaryloxyaryl type compound with formula (R—CH═CH—(X)—O) n —Ar—Q, 
       where Q is —N═C═O or a precursor thereof; —NH 2 or —CON 3 ; —COCl or its precursor; —COOH; —N═C═S; or —CH 2 Y, where Y is Cl or Br or I or methylsulphonyloxy or paratoluenesulphonyloxy or 3,5-dimethylphenylsulphonyloxy and where:  
       n is in the range 1 to 20;  
       R is hydrogen or a linear or branched alkyl group or a linear or branched alkoxy group or hydroxyl or an aryl group, optionally substituted;  
       X is a linear alkyl group carrying more than one carbon atom or a branched alkyl group, or an aryl group, optionally substituted with at least one group selected from the group consisting of hydrogen, alkyl, alkoxy, hydroxyl and trihalogenoalkyl groups; and  
       Ar is an aryl or polyaryl group, optionally substituted with at least one hydrogen atom or with at least one group selected from the group consisting of alkyl, alkoxy, hydroxyl, trihalogenoalkyl, silyl, thiol, amino, aminoalkyl, amide, nitro, nitrosamino, N-amino, aldehyde, acid and ester groups,  
       excluding the following compounds: 4-allyloxyaniline, 4-allyloxybenzoic acid, its acid chloride, and 4-allyloxyphenylisocyanate.  
     
     
       2. A chiral compound which can be obtained by hydrosilylation of the chiral compound of  claim 1  to transform at least a portion of the alkenyl moieties R—CH═CH— using a silane (R 1 , R 2 , R 3 )Si—H generally in the presence of a metallic complex derived from platinum or rhodium to (R 1 , R 2 , R 3 )—Si—CH(R)—CH 2 — moieties, where: 
       R 1  is hydrogen or an alkoxy group or a halogen or an amino or alkylamino group;  
       R 2  and R 3 , which may be identical to or different from R 1 , are alkoxy, hydroxyl, trihalogenoalkyl, linear or branched alkyl or aryl groups;  
       R is hydrogen or a linear or branched alkyl group or a linear or branched alkoxy group or a hydroxyl group or an aryl group optionally substituted.  
     
     
       3. A chiral compound which can be obtained by hydrosilylation of the bifunctional alkenyloxyaryl or alkenylaryloxyaryl type compound with formula (R—CH═CH—(X)—O) n —Ar—Q, 
       where Q is —N═C═O or a precursor thereof: —NH 2  or —CON 3 ; —COCl or its precursor;  
       —COOH; —N═C═S; or —CH 2 Y, where Y is Cl or Br or I or methylsulphonyloxy or paratoluenesulphonyloxy or 3,5-dimethylphenylsulphonyloxy and where:  
       n is in the range 1 to 20;  
       R is hydrogen or a linear or branched alkyl group or a linear or branched alkoxy group or hydroxyl or an aryl group, optionally substituted;  
       X is a linear alkyl group carrying more than one carbon atom or a branched alkyl group, or an aryl group, optionally substituted with at least one group selected from the group consisting of hydrogen, alkyl, alkoxy, hydroxyl and trihalogenoalkyl groups; and  
       Ar is an aryl or polyaryl group, optionally substituted with at least one hydrogen atom or with at least one group selected from the group consisting of alkyl, alkoxy, hydroxyl, trihalogenoalkyl, silyl, thiol, amino, aminoalkyl, amide, nitro, nitrosamino, N-amino, aldehyde, acid and ester groups,  
       excluding the following compounds: 4-allyloxyaniline, 4-allyloxybenzoic acid, its acid chloride, and 4-allyloxyphenylisocyanate to transform at least a portion of alkenyl moieties R—CH+CH— using a silane (R 1 , R 2 , R 3 )—Si—H in the presence of a metallic complex derived from platinum or rhodium to (R 1 , R 2 , R 3 )—Si—CH(R)—CH 2 — moieties, where:  
       R 1  is hydrogen or an alkoxy group or a halogen or an amino or alkylamion group;  
       R 2  and R 3 , which may be identical to or different from R 1 , are alkoxy, hydroxyl, trihalogenoalkyl, linear or branched alkyl or aryl groups;  
       then by reacting at least one hydrogen of an alcohol, amine or thiol function of at least one chiral unit of a product with at least one group Q of the hydrosilylated bifunctional alkenyloxyaryl or alkenylaryloxyaryl type compound.  
     
     
       4. A chiral compound according to  claim 1 , in which said chiral unit of a product is a glycosidic unit of a product selected from holosides, heterobolosides, oligosides, cyclooligosides, heterooligosides, polyosides, heteropolyosides, enzymes and proteins. 
     
     
       5. A chiral compound according to  claim 2 , wherein the bifunctional compound is parapent-4-enoxybenzoic acid. 
     
     
       6. A chiral compound according to  claim 1 , wherein the bifunctional compound is selected from the group consisting of parapent-4-enoxybenzoic acid, the acid chloride thereof, parapent-4-enoxybenzoylazide, and parapent-4-enoxyphenylisocyanate. 
     
     
       7. A chiral compound according to  claim 5 , wherein the bifunctional compound is parapent-4-enoxybenzoic acid. 
     
     
       8. A chiral compound according to  claim 1 , wherein the bifunctional compound is parapent-4-enoxybenzoic acid. 
     
     
       9. A chiral compound according to  claim 4 , wherein the bifunctional compound is parapent-4-enoxybenzoic acid. 
     
     
       10. A chiral compound according to  claim 2 , in which said chiral unit of a product is a glycosidic unit of a product selected from holosides, heteroholosides, oligosides, cyclooligosides, heterooligosides, polyosides, heteropolyosides, enzymes and proteins. 
     
     
       11. A chiral compound according to  claim 3 , in which said chiral unit of a product is a glycosidic unit of a product selected from holosides, heteroholosides, oligosides, cyclooligosides, heterooligosides, polyosides, heteropolyosides, enzymes and proteins. 
     
     
       12. A chiral compound obtained by hydrosilylation of another chiral compound obtained by reaction of at least one hydrogen of an alcohol, amine, or thiol function of at least one chiral unit of a product with at least one group Q of a bifunctional compound wherein the bifunctional compound is an alkenyloxyaryl or alkenylaryloxyaryl type compound with formula (R—CH═CH—(X)—O) n —Ar—Q, 
       where Q is —N═C═O or a precursor thereof; —NH 2  or —CON 3 ; —COCl or its precursor; —COOH; —N═C═S; or —CH 2 Y, where Y is Cl or Br or I or methylsulphonyloxy or paratoluenesulphonyloxy or 3,5-dimethylphenylsulphonyloxy and where:  
       n is in the range 1 to 20;  
       R is hydrogen or a linear or branched alkyl group or a linear or branched alkoxy group or hydroxyl or an aryl group, optionally substituted;  
       X is a linear alkyl group carrying more than one carbon atom or a branched alkyl group, or an aryl group, optionally substituted with at least one group selected from the group consisting of hydrogen, alkyl, alkoxy, hydroxyl and trihalogenoalkyl groups; and  
       Ar is an aryl or polyaryl group, optionally substituted with at least one hydrogen atom or with at least one group selected from the group consisting of alkyl, alkoxy, hydroxyl, trihalogenoalkyl, silyl, thiol, amino, aminoalkyl, amide, nitro, nitrosamino, N-amino, aldehyde, acid and ester groups,  
       excluding the following compounds: 4-allyloxyaniline, 4-allyloxybenzoic acid, its acid chloride, and 4-allyloxyphenylisocyanate; wherein,  
       the reaction transforms at least a portion of the alkenyl moieties R—CH═CH— using a silane (R 1 , R 2 , R 3 )—Si—H in the presence of a metallic complex derived from platinum or rhodium to (R 1 , R 2 , R 3 )—Si—CH(R)—CH 2 — moieties, where:  
       R 1  is hydrogen or an alkoxy group or a halogen or an amino or alkylamino group;  
       R 2  and R 3 , which may be identical to or different from R 1 , are alkoxy, hydroxyl, trihalogenoalkyl, linear or branched alkyl or aryl groups; and  
       R is hydrogen or a linear or branched alkyl group or a linear or branched alkoxy group or a hydroxyl group or an aryl group optionally substituted.  
     
     
       13. The chiral compound according to  claim 12  in which said chiral unit of a product is a glycosidic unit of a product selected from holosides, heteroholosides, oligosides, cyclooligosides, heterooligosides, polyosides, heteropolyosides, enzymes and proteins. 
     
     
       14. The chiral compound according to  claim 12  wherein the bifunctional compound is selected from the group consisting of parapent-4-enoxybenzoic acid, the acid chloride thereof, parapent-4-enoxybenzoylazide, and parapent-4-enoxyphenylisocyanate. 
     
     
       15. The chiral compound according to  claim 12 , wherein the bifunctional compound is parapent-4-enoxybenzoic acid. 
     
     
       16. The chiral compound according to  claim 13 , wherein the bifunctional compound is parapent-4-enoxybenzoic acid. 
     
     
       17. The chiral compound according to  claim 14 , in which said chiral unit of a product is a glycosidic unit of a product selected from holosides, heteroholosides, oligosides, cyclooligosides, heterooligosides, polyosides, heteropolyosides, enzymes and proteins. 
     
     
       18. A compound according to  claim 10 , wherein the bifunctional compound is parapent-4-enoxybenzoic acid. 
     
     
       19. The chiral compound according to  claim 6 , in which said chiral unit of a product is a glycosidic unit of a product selected from holosides, heteroholosides, oligosides, cyclooligosides, heterooligosides, polyosides, heteropolyosides, enzymes and proteins. 
     
     
       20. The chiral compound according to  claim 3 , wherein the bifunctional compound is selected from the group consisting of parapent-4-enoxybenzoic acid, the acid chloride thereof, parapent-4-enoxybenzoylazide, and parapent-4-enoxyphenylisocyanate. 
     
     
       21. The chiral compound according to  claim 11 , wherein the bifunctional compound is parapent-4-enoxybenzoic acid. 
     
     
       22. The chiral compound according to  claim 20 , in which said chiral unit of a product is a glycosidic unit of a product selected from holosides, heteroholosides, oligosides, cyclooligosides, heterooligosides, polyosides, heteropolyosides, enzymes and proteins. 
     
     
       23. The chiral compound according to  claim 2  wherein the bifunctional compound is selected from the group consisting of parapent-4-enoxybenzoic acid, the acid chloride thereof, parapent-4-enoxybenzoylazide, and parapent-4-enoxyphenylisocyanate. 
     
     
       24. The chiral compound according to  claim 23 , in which said chiral unit of a product is a glycosidic unit of a product selected from holosides, heteroholosides, oligosides, cyclooligosides, heterooligosides, polyosides, heteropolyosides, enzymes and proteins.